Methods and chemistry for providing initial conformal electrochemical deposition of copper in sub-micron features

ABSTRACT

A method for electrolytically repairing a copper seed layer. The method includes positioning the seed layer in fluid communication with a low conductivity seed layer repair solution, wherein the low conductivity seed layer repair solution includes a copper concentration of less than about 20 g/l, a pH of less than about 4, a chlorine ion concentration of between about 20 ppm and about 100 ppm, and an additive organic surfactant configured to suppress a copper deposition rate in the concentration range of 200 ppm to 2000 ppm. The method further includes applying a seed layer repair bias configured to generate a current density of less than about 5 mA/cm 2  across the seed layer and cleaning the repaired seed layer in pure water containing less than 1 ppm chloride ions.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims benefit of U.S. provisional patent application Ser. No. 60/510,190, filed Oct. 10, 2003, which is herein incorporated by reference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

Embodiments of the present invention generally relate to a method and chemistry for electrolytically repairing a seed layer deposited onto a semiconductor substrate.

2. Description of the Related Art

Metallization for sub-quarter micron sized features is a foundational technology for present and future generations of integrated circuit manufacturing processes. In devices such as ultra large scale integration-type devices, i.e., devices having integrated circuits with more than a million logic gates, the multilevel interconnects that lie at the heart of these devices are generally formed by filling high aspect ratio interconnect features with a conductive material (e.g., copper, gold, silver, or aluminum). Conventionally, deposition techniques such as chemical vapor deposition (CVD) and physical vapor deposition (PVD) have been used to fill these interconnect features. However, as the interconnect sizes decrease and aspect ratios increase, void-free interconnect feature fill via conventional metallization techniques becomes increasingly difficult via CVD and PVD techniques. As a result thereof, plating techniques, such as electrochemical plating (ECP) and electroless plating have emerged as viable processes for filling sub-quarter micron sized high aspect ratio interconnect features in integrated circuit manufacturing processes.

In an ECP process, for example, sub-quarter micron sized high aspect ratio features formed into the surface of a substrate (or a dielectric layer deposited thereon) may be efficiently filled with a conductive material, such as copper. Most ECP processes are generally two stage processes, wherein a seed layer is first formed over the surface features of the substrate (this process may be performed in a separate system), and then the substrate surface features are exposed to an electrolyte solution while an electrical bias is simultaneously applied between the substrate surface and an anode positioned within the electrolyte solution. The electrolyte solution is generally rich in ions to be plated onto the surface of the substrate, and therefore, the application of the electrical bias operates to drive a reductive reaction that reduces the metal ions and precipitates the respective metal. Upon precipitating, the metal plates onto the seed layer to form a film. This process may be continued until the thickness of the layer reaches a desired thickness.

As noted above, conventional plating practices include depositing a copper seed layer via physical vapor deposition (PVD), chemical vapor deposition (CVD), or atomic layer deposition (ALD) onto a diffusion barrier layer (e.g., tantalum or tantalum nitride). However, as the feature sizes become smaller, it becomes extremely difficult to have adequate seed step coverage with PVD techniques, as discontinuous islands of copper agglomerates are often obtained close to the feature bottom in high aspect ratio features with PVD techniques. For CVD techniques, a thick copper layer (e.g., >200 Å) over the field is generally needed to have continuous sidewall coverage throughout the depth of high aspect ration features, which often causes the throat of the feature to close before the feature sidewalls are covered. As such, CVD techniques are also prone to generating discontinuities in the seed layer when the deposition thickness on the field is reduced to prevent throat closure. These discontinuities in the seed layer have been shown to cause plating defects in the layers plated over the seed layer.

Therefore, there is a need for a method and chemistry for electrochemically repairing discontinuities in a seed layer.

SUMMARY OF THE INVENTION

The present invention generally provides a method for repairing discontinuities in copper seed layers formed on substrates. The method includes using an acidic electrolytic solution to plate a copper repair layer over copper seed layer having discontinuities therein in a manner that operates to cover the discontinuities. The chemistry of the invention generally includes an electrolytic seed repair solution that has a pH of less than about 4.

Embodiments of the invention further provide a method for electrolytically repairing a copper seed layer. The method includes positioning the substrate having the seed layer formed thereon in fluid communication with a low conductivity seed layer repair solution, which includes a copper concentration of less than about 20 g/l, a pH of less than about 4, a chlorine ion concentration of between about 10 ppm and about 100 ppm, and an additive organic surfactant configured to suppress a copper deposition rate. The method further includes applying a seed layer repair bias configured to generate a current density of less than about 5 mA/cm² across the seed layer.

Embodiments of the invention further provide a method for filling a semiconductor feature having a seed layer deposited thereon with a conductive material. The method includes positioning a substrate having a seed layer formed thereon in a first plating solution having a pH of less than about 4 and a copper concentration of less than about 10 g/l, applying a first plating bias to the seed layer to plate a metal onto discontinuities in the seed layer, the first plating bias having a first current density across the seed layer of less than about 5 mA/cm². The method further includes removing the substrate from the first plating solution, cleaning the seed layer of residual chemical constituents from the first plating with a cleaning solution having less than about 1 ppm of chlorine ions, positioning the seed layer in a second plating solution, the second plating solution being different from the first plating solution, and applying a second plating bias to the seed layer to deposit a feature fill layer, wherein the second plating bias is configured to generate a second current density across the seed layer that is greater than the first current density.

Embodiments of the invention further provide a method for plating a metal onto a discontinuous seed layer. The method includes repairing the discontinuous seed layer by immersing the seed layer in a low conductivity electrolytic plating solution having a pH of less than about 4, and applying a bias to the seed layer that is configured to generate a current density of between about 2 mA/cm² and about 5 mA/cm² across the seed layer. The method further includes removing the seed layer from the low conductivity electrolytic bath, rinsing the seed layer of residual chemicals, immersing the seed layer in a conductive gap fill electrolytic solution having a pH of between about 2 and about 6, and applying a gap fill bias to the seed layer to electrolytically fill features formed thereon, the gap fill bias being configured to generate a current density of between about 5 mA/cm² and about 40 mA/cm².

BRIEF DESCRIPTION OF THE DRAWINGS

So that the manner in which the above recited features of the present invention can be understood in detail, a more particular description of the invention, briefly summarized above, may be had by reference to embodiments, some of which are illustrated in the appended drawings. It is to be noted, however, that the appended drawings illustrate only typical embodiments of this invention and are therefore not to be considered limiting of its scope, for the invention may admit to other equally effective embodiments.

FIG. 1 illustrates a top plan view of an electrochemical plating system capable of conducting the method of the invention.

FIG. 2 illustrates a partial sectional and partial perspective view of an exemplary plating cell used in the method of the invention.

FIG. 3 illustrates a graph of the electrochemical polarization for acidic baths for various suppressors.

FIG. 4 illustrates a graph of the effect of 1 ppm of chlorine on suppressor post clean effectiveness.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

FIG. 1 illustrates a top plan view of an ECP system 100 of the invention. ECP system 100 includes a factory interface 130, which is also generally termed a substrate loading station. Factory interface 130 includes a plurality of substrate loading stations configured to interface with substrate containing cassettes 134. A robot 132 is positioned in factory interface 130 and is configured to access substrates contained in the cassettes 134. Further, robot 132 also extends into a link tunnel 115 that connects factory interface 130 to processing mainframe or platform 113. The position of robot 132 allows the robot to access substrate cassettes 134 to retrieve substrates therefrom and then deliver the substrates to one of the processing cells 114, 116 positioned on the mainframe 113, or alternatively, to an annealing station 135. Similarly, robot 132 may be used to retrieve substrates from the processing cells 114, 116 or the annealing chamber 135 after a substrate processing sequence is complete. In this situation robot 132 may deliver the substrate back to one of the cassettes 134 for removal from system 100.

The processing mainframe 113 includes a substrate transfer robot 120 centrally positioned thereon. Robot 120 generally includes one or more arms/blades 122, 124 configured to support and transfer substrates thereon. Additionally, the robot 120 and the accompanying blades 122, 124 are generally configured to extend, rotate, and vertically move so that the robot 120 may insert and remove substrates to and from a plurality of processing locations 102, 104, 106, 108, 110, 112, 114, 116 positioned on the mainframe 113. Similarly, factory interface robot 132 also includes the ability to rotate, extend, and vertically move its substrate support blade(s), while also allowing for linear travel along the robot track that extends from the factory interface 130 to the mainframe 113. Generally, process locations 102, 104, 106, 108, 110, 112, 114, 116 may be any number of processing cells utilized in an electrochemical plating platform. More particularly, the process locations may be configured as electrochemical plating cells, rinsing cells, bevel clean cells, spin rinse dry cells, substrate surface cleaning cells (which collectively includes cleaning, rinsing, etching, and ozone treatment cells, etc.), electroless plating cells, metrology inspection stations, and/or other processing cells that may be beneficially used in conjunction with a plating platform. Each of the respective processing cells and robots are generally in communication with a process controller 111, which may be a microprocessor-based control system configured to receive inputs from both a user and/or various sensors positioned on the system 100 and appropriately control the operation of system 100 in accordance with the inputs.

In the exemplary plating system illustrated in FIG. 1, the processing locations may be configured as follows. Processing locations 114 and 116 may be configured as an interface between the wet processing stations on the mainframe 113 and the dry processing regions in the link tunnel 115, annealing chamber 135, and the factory interface 130. The processing cells located at the interface locations may be spin rinse dry cells and/or substrate cleaning cells, for example. More particularly, each of locations 114 and 116 may include both a spin rinse dry cell and a substrate cleaning cell in a stacked configuration. Locations 102, 104, 110, and 112 may be configured as plating cells, either electrochemical plating cells or electroless plating cells, for example. Locations 106, 108 may be configured as substrate bevel cleaning cells. Additional configurations and implementations of an electrochemical processing system are illustrated in commonly assigned U.S. patent application Ser. No. 10/435,121 filed on Dec. 19, 2002 entitled “Multi-Chemistry Electrochemical Processing System”, which is incorporated herein by reference in its entirety. Regardless of the configuration of the respective plating cells, ECP system 100 is generally configured to provide multiple plating cells on a single platform, wherein each of the multiple plating cells is capable of having a different chemistry therein from each of the other plating cells on the platform.

FIG. 2 illustrates a partial perspective and sectional view of an exemplary plating cell 200 that may be implemented in processing locations 102, 104, 110, and 112 (or other processing locations on system 100 as desired). The electrochemical plating cell 200 generally includes an outer basin 201 and an inner basin 202 positioned within outer basin 201. Inner basin 202 is generally configured to contain a plating solution that is used to plate a metal, e.g., copper, onto a substrate during an electrochemical plating process. During the plating process, the plating solution is generally continuously supplied to inner basin 202, and therefore, the plating solution continually overflows the uppermost point (generally termed a “weir”) of inner basin 202 and is collected by outer basin 201 and drained therefrom for chemical management and/or recirculation.

Plating cell 200 is generally positioned at a tilt angle, i.e., a frame portion 203 of plating cell 200 is generally elevated on one side such that the components of plating cell 200 are tilted between about 3° and about 300 from horizontal, or generally between about 4° and about 10°. The frame member 203 of plating cell 200 supports an annular base member 204 on an upper portion thereof, and since frame member 203 is elevated on one side, the upper surface of base member 204 is generally tilted from the horizontal at an angle that corresponds to the tilt angle of frame member 203 relative to a horizontal position.

Base member 204 includes an annular or disk shaped recess formed into a central portion thereof, the annular recess being configured to receive a disk shaped anode member 205. Base member 204 further includes a plurality of fluid inlets/drains 209 extending from a lower surface thereof. Each of the fluid inlets/drains 209 are generally configured to individually supply or drain a fluid to or from either the anode compartment or the cathode compartment of plating cell 200. Anode member 205 generally includes a plurality of slots 207 formed therethrough, wherein the slots 207 are generally positioned in parallel orientation with each other across the surface of the anode 205. The parallel orientation allows for dense fluids generated at the anode surface to flow downwardly across the anode surface and into one of the slots 207.

Plating cell 200 further includes a membrane support assembly 206. Membrane support assembly 206 is generally secured at an outer periphery thereof to base member 204, and includes an interior region configured to allow fluids to pass therethrough. A membrane 208, which may be a cationic membrane, is stretched across the support 206 and operates to fluidly separate a catholyte chamber (positioned adjacent the substrate being plated) and anolyte chamber (positioned adjacent the anode electrode in the cell) of the plating cell. The membrane support assembly 206 may include an o-ring type seal positioned near a perimeter of the membrane 208, wherein the seal is configured to prevent fluids from traveling from one side of the membrane 208 secured on the membrane support 206 to the other side of the membrane 208.

A diffusion plate 210, which is generally a porous ceramic disk member is configured to generate a substantially laminar flow or even flow of fluid in the direction of the substrate being plated, is positioned in the cell between membrane 208 and the substrate being plated. The diffusion plate 210 is generally manufactured from an electrically insulating material, and as such, the diffusion plate 210 also operates to control the electric field generated between the anode and the substrate. Embodiments of the invention are not limited to ceramic diffusion members, as other electrically insulative porous materials that are non-reactive with electrochemical processing fluid may also be used. Additionally, embodiments of the invention further contemplate that electrically insulative materials that are not porous may be used, as holes or bores may be formed therein to allow fluid to flow therethrough.

The exemplary plating cell and the components thereof are further illustrated in commonly assigned U.S. patent application Ser. No. 10/268,284, which was filed on Oct. 9, 2002 under the title “Electrochemical Processing Cell”, claiming priority to U.S. Provisional Application Ser. No. 60/398,345, which was filed on Jul. 24, 2002, both of which are incorporated herein by reference in their entireties. Additional embodiments of the plating cell are discussed in commonly assigned U.S. patent application Ser. No. 10/627,336, filed on Jul. 24, 2003, entitled “Electrochemical Processing Cell”, which is also incorporated by reference herein in its entirety.

In operation, ECP system 100 and plating cell 200 may be used to electrolytically fill high aspect ratio features with a conductive metal. More particularly, ECP system 100 and plating cell 200 may be used to electrolytically repair or patch a seed layer deposited onto a substrate having high aspect ratio features thereon in a first electrolytic bath. Thereafter, ECP system 100 and plating cell 200 may be used to electrolytically plate a conductive layer over the repaired or patched seed layer to fill the high aspect ratio features in a second electrolytic bath, wherein the first electrolytic bath is different from the first electrolytic bath. As noted above, the seed layer (and generally an underlying barrier layer) is generally deposited in a separate deposition apparatus, such as a PVD or CVD system.

The process of repairing the seed layer and filling the features generally begins with a substrate immersion process. The immersion process includes securing the substrate to be plated to a cathode electrode, often termed a contact ring, for processing. Exemplary contact rings are illustrated in commonly assigned U.S. Pat. No. 6,251,236, entitled “Cathode Contact Ring for Electrochemical Deposition”, and commonly assigned U.S. patent application Ser. No. 10/278,527, entitled “Plating Uniformity Control by Contact Ring Shaping” filed on Oct. 22, 2002, both of which are hereby incorporated by reference in their entirety. The substrate is secured to the contact ring such that a seed layer deposited on the substrate is in electrical contact with the electrical contact elements or pins of the contact ring. Once the substrate is secured to the contact ring, the substrate is immersed into a first electrolytic plating solution contained in a plating cell, wherein the first electrolytic plating solution is configured as a seed repair plating solution. The process of immersing the substrate into the plating solution generally includes rotating, tilting, and/or vertically actuating the contact ring having the substrate secured thereto into the plating solution, as described in commonly assigned U.S. patent application Ser. No. 10/266,477, entitled “Tilted Electrochemical Plating Cell With Constant Wafer Immersion Angle”, filed on Oct. 7, 2002 and commonly assigned U.S. Provisional Patent Application Ser. No. 60/448,575, entitled “Wafer Immersion Mechanism”, filed on Feb. 18, 2003, both of which are hereby incorporated by reference in their entirety. The process of immersing the substrate into the electrolytic solution may also include applying an immersion bias to the substrate, as acidic electrolytic solutions have been shown to etch seed layers, thus compounding the problem of discontinuities in the seed layer. The immersion bias will generally be a forward or plating bias that is configured to overcome the etching effect of acidic solutions during the immersion process. The process of supplying and controlling an immersion bias is described in commonly assigned U.S. patent application Ser. No. 10/135,546, entitled “Apparatus and Method for Regulating the Electrical Power Applied to a Substrate During Immersion”, filed on Apr. 29, 2002.

Once the substrate is immersed in the seed repair solution, a plating bias is generally applied to the substrate. The plating bias is configured to drive a reduction reaction between the anode of the plating cell, which is in electrical communication with the anodic terminal of the power supply, and the cathode contact ring, which is in electrical communication with the seed layer on the substrate. The reduction reaction causes metal ions in the electrolytic solution (the seed repair solution) to plate onto the substrate. However, in order to facilitate plating on the discontinuous areas of the seed layer, i.e., the void areas that generally reside on the sidewalls of high aspect ratio features, a low conductivity acidic seed layer repair solution is utilized. More particularly, in order to facilitate an electrolytic copper seed layer repair process, the acidic seed layer repair electrolyte solution includes a low conductivity copper sulfate solution having a pH of less than or equal to about 4, and a copper concentration of less than or equal to about 20 g/l. Further, the pH may be between about 1.5 and about 4, between about 1.5 and about 3, between about 1 and about 2.5, or between about 1.5 and about 2.5, for example, for this embodiment, along with the other embodiments of the invention. As noted below, solutions having a pH of greater than about 4 tend to generate unwanted precipitates, and as such, they are not preferred for the seed layer repair solution. The inventors have found that these concentrations are capable of uniform copper deposition current distribution inside micro recessed high aspect ratio features. The current density applied to the substrate during the seed repair process is generally between 1 mA/cm² and about 5 mA/cm², for example, and the repair process generally has a duration of between about 6.0 seconds and about 55 seconds to ensure about a 100 to about a 200 angstrom thick repair layer. More preferably, the current density is between about 1 mA/cm2 and about 3 mA/cm2, and the duration is between about 9 and about 42 seconds to ensure a 100-150 angstrom thick repair layer. The conductivity of the plating solution containing about 5 g/l Cu and about X g/l of H₂SO₄ at room temperature have been measured. The conductivity, Y in units of milli Siemens per centimeter, can be expressed as a function of the H₂SO₄ concentration X as follows: Y=3.859 X+6.874, where the H₂SO₄ concentration is in the range of between about 0 and about 1 g/l. Further, the addition of 50 ppm Cl and the suppressor in the concentration range of interest does not change the solution electrical conductivity.

In another embodiment of the invention, the seed repair solution additionally includes a particular concentration of suppressor molecules, along with between about loppm and about 100 ppm of chlorine ions, which operates to maximize electrochemical polarization and obtain a fine grained smooth deposited seed layer repair layer. The class of suppressors capable of supporting this process includes polyethylene glycol having a molecular weight of greater than about 600, and copolymers of ethylene oxide-propylene oxide, and their derivatives having a molecular weight of greater than about 1000. The concentration of the suppressor in the seed repair solution is generally between about 100 mg/l and about 2000 mg/l, for example.

The seed layer repair solutions of the invention are generally formulated to facilitate copper deposition along the entire sidewall of high aspect ratio features via a more uniform current distribution that is achieved by reducing the copper and acid concentrations in the seed repair solution. For example, the inventors have tested a plating solution containing approximately 5-10 g/l of copper, 0.5 g/l of acid (thus generating a pH of about 2.30), about 50 ppm of chlorine+ions, and an additive suppressor compound. Implementation of this plating solution in a seed layer repair plating process wherein a current density of less than about 5 mA/cm² was applied for less than about 55 seconds provided complete sidewall coverage and a smooth continuous copper layer over the interior surfaces of the features when viewed on a micrograph and compared to a similar sample processed under similar conditions without the seed layer repair process. Additionally, the acidic seed layer repair solution provided improved results over conventional alkaline seed layer repair solutions, and further, eliminated the requirement for additional safety precautions, e.g., acidic neutralization chemicals, that are necessary when working with alkaline based plating solutions. Further still, since acidic plating solutions are generally used for gap fill solutions, the acidic seed layer repair solution required no additional chemical management tools or processes, as the same constituents are used in the seed layer repair solution, only in different concentrations. Additionally, in a similar test using similar processing parameters, a plating solution containing about 5 g/l of copper, acid sufficient to generate a pH of about 3.1, about 50 ppm of chlorine ions, and an additive suppressor was used under similar processing conditions, and similar results were obtained, i.e., complete sidewall coverage and a smooth continuous copper layer over the interior surfaces of the features when viewed on a micrograph.

Further, with regard to the use of suppressor chemistry noted above, it is generally known that the copper deposition rate in acidic solutions occurs at a relative fast rate as a result of the high exchange current density provided by the acidic bath. Further, deposition from acidic baths without organic additives to suppress the copper growth rate are known to be overly rough for semiconductor processing applications involving high aspect ratio features. Therefore, in order for the acidic seed layer repair solutions noted above to be effective, i.e., to provide acceptable plating rates, smoothness, and coverage in high aspect ratio features, the addition of organic surfactants configured to suppress the copper deposition rate is generally required. The effectiveness of the surfactants in the acidic solution are evidenced by the electrochemical polarization characteristics illustrated in FIG. 3, which is a plot of the Cu deposition current vs. Cu deposition potential, wherein the negative sign for the current/potential indicates that both the current and the potential are cathodic. Higher cathodic polarization (more negative potential corresponding to any particular deposition current) will improve the deposition smoothness by increasing the Cu nucleation rate through over saturation of Cu ions. The addition of suppressor molecules, such as PEG (polyethylene glycol) and EO (ethylene oxide)/PO (propylene oxide) co-polymer molecules, has been shown to significantly shift the Cu deposition potential cathodically as compared to the make-up plating solution containing no additives. Therefore, suppressor addition will significantly improve the Cu deposit smoothness. The degree of improvement depends on the suppressor molecular nature. For example, increasing the molecular weight from between about 600 and about 2000, or more particularly, between about 600 and about 1000, has been shown to further increase the cathodic polarization, and hence the deposit smoothness. Also, EO/PO co-polymers with different EO/PO percentages and molecular arrangements provide even stronger cathodic polarization than PEG molecules, so they are also candidates as suitable suppressors. Exemplary suppressors that may be used in the acidic seed layer repair solution of the invention include polyethylene glycol, copolymers of ethylene oxide-propylene oxide, and any derivatives of the above molecules.

Once the seed layer repair step or layer has been deposited, the substrate is removed from the plating cell. The substrate is then transferred to a second plating cell for subsequent processing, which generally includes another electrochemical plating process that is configured to completely fill the features on the substrate. The second plating cell generally contains a second plating solution, which is generally termed a gap fill solution. The gap fill solution is generally different from the seed layer repair solution, and more particularly, the gap fill solution generally includes additional plating additives therein, e.g., levelers and accelerators.

However, since the gap fill solution contains different chemical constituents than the seed repair solution, the substrate is generally cleaned between the seed repair plating process and the gap fill plating process, as constituents from the seed repair plating solution may adhere to the substrate surface when it is removed from the seed repair plating cell and subsequently contaminate the gap fill plating solution. The substrate cleaning process may generally include transferring the substrate from the seed repair plating cell to one of the spin rinse dry (SRD) cells of the ECP system 100. Once the substrate is positioned in the SRD a rinsing solution, such as deionized water, may be dispensed onto the substrate surface to remove any remaining seed layer repair chemical constituents from the surface of the substrate.

Additionally, the process of cleaning the substrate between the seed layer repair and gap fill plating steps may further include applying agitation to the substrate to facilitate cleaning. The agitation may be sonic, ultra sonic, or megasonic, for example. Further, in order to facilitate optimal removal of the seed layer repair chemical constituents from the surface of the substrate, the rinsing solution, which may be deionized water, for example, generally contains less than about 1 ppm or less than about 1 mg/l of chlorine. The lack of chlorine from the rinsing or cleaning solution is important to the operation of the invention, as chlorine concentrations greater than about 1 ppm in the rinsing solution have been shown to make removal of the suppressor used in the seed repair bath from the substrate surface difficult, which results in challenges to void free gap fill, as the presence of the residual suppressors prevents proper filling.

For example, FIG. 4 illustrates the effect of 1 ppm of chlorine in the suppressor post clean effectiveness. The suppressor residual on the plated wafer surface is simulated by soaking the plated Cu film on top of a platinum disk electrode (hereafter called Cu disk electrode) in the seed repair solution for 30 seconds. The treated Cu disk electrode is then cleaned in post-seed-repair cleaning solutions. The effectiveness of the cleaning process is checked by performing a polarization study in a plating solution containing no organic additives. The presence or absence of residual suppressors after cleaning can be seen by the magnitude of Cu plating current during cathodic deposition. The polarization curve on a clean Cu disk electrode that is not soaked in the post-seed-repair solution is plotted (bottom curve) as reference, this curve exhibits the typical behavior of Cu deposition in the absence of any organic additives.

The top curve in FIG. 4 represents a polarization curve taken immediately following the soaking of the Cu disk electrode in post-seed-repair solution. Very strong suppression of Cu deposition current due to suppressor residual on Cu disk electrode is illustrated by this curve. Additionally, the degree of current suppression exerted by the surface suppressor residual is comparable to the suppression provided by the suppressor molecules in the seed repair solution. The remaining three polarization curves between the top and bottom curves were obtained after cleaning the surface suppressor residual in the post-seed-repair solutions containing 1 ppm chloride ion for a time period from 60 seconds to 240 seconds. It is apparent that a large part of the residual suppressor still remains on the Cu disk electrode surface even after 240 seconds of cleaning, and the residual amount was not further reduced by increasing the cleaning time from 120 seconds to 240 seconds. Therefore, it can be concluded that the presence of even 1 ppm chloride ion in the cleaning solution will prevent the effective removal of suppressor residual on the wafer surface. Further, the rinsing solution generally contains no organic solvents, such as alcohol or acetone, for the same reasons the solution does not contain chlorine.

Once the substrate is cleaned of the remaining surface organics, then the substrate may be processed in a gap fill plating solution. The gap fill plating solution is generally contained in a plating cell that is different or separate from the plating cell containing the seed layer repair solution. In the gap fill cell, an acidic plating solution is generally used to plate copper into the features to fill the features without generating interior voids in the fill layer. The gap fill solution may include between about 30 and about 60 g/l of Cu, between about 5 and about 100 g/l of acid, between about 20 and about 100 ppm of Cl ions, between about 5 and about 30 ppm of an additive accelerator, between about 100 and about 1000 ppm of an additive suppressor, and between about 1 and about 6 ml/l of an additive leveler. A general duration for a gapfill process is in the range of between about 10 and about 50 seconds using a plating current density of about 5 mA/cm², however, the inventors note that the gapfill duration may be decreased if the plating process can be conducted at higher plating rates without sacrificing fill or defect parameters.

Once the gap fill process has been completed, the substrate may be removed from the gap fill plating cell and transferred to another cell on ECP system 100 for further processing. Additional processing steps include, for example, but are not limited to an additional bulk plating step, an edge bead removal process, a spin rinse dry process, a surface clean process, and/or an annealing process. Once the post-plating processes are completed, the substrate may be transferred out of ECP system 100 via robots 120, 132 and into substrate cassettes 134.

The seed layer repair process of the invention is generally three step process in nature. The first fundamental step is wafer immersion into the repair solution, where two important requirements must be met. First, the wafer must be protected against corrosion, and therefore, a cathodic potential bias must be applied, and the potential should be such that the cathodic current density is greater than or equal to about 1 mA/cm². In addition, accelerators should not be present in the repair solution since accelerators induce Cu corrosion. Further, the lower limit for the suppressor concentration should be high enough to ensure that the repair solution possesses high enough anti-corrosion capability. Second, the repair solution should not generate excessive gas bubbles upon wafer immersion. Since the bubble generation tendency generally increases with higher suppressor concentrations, the suppressor concentration should be limited in order to minimize plating defects.

The method or process of the invention also generally includes a two step plating process, wherein the first step is a seed layer repair step (as discussed above) and the second step is a feature fill step. The repair and fill steps are generally conducted in separate plating cells using separate and different plating solutions and processing parameters. The method of the invention generally includes providing a substrate having a seed layer thereon to a first plating cell. The substrate provided to the cell is generally a clean dry substrate with minimal oxidation of the seed layer. Alternatively, the substrate provided to the first plating cell may be treated with a pre-seed layer repair solution, such as a solution configured to improve the wetability of the substrate or a plating solution additive configured to promote the seed layer repair process.

The electrochemical plating solution used in the seed layer repair process, as described above, generally includes a copper source, an acid source, a chlorine ion source, and at least one plating solution additive, i.e., levelers, suppressors, accelerators, antifoaming agents, etc. Specifically, the repair solution may contain the following constituents: copper (between about 5 and about 20 g/l, preferably between about 5 and about 10 g/l), an acid (between about 0.1 and about 5 g/l, preferably between about 0.1 and about 1.0 g/l), a chlorine ion source (between about 20 and about 100 ppm, preferably between about 20 and about 50 ppm), and an additive suppressor (between about 100 and about2000 ppm for PEG, EO/PO co-polymers, and their derivatives. The lower limit imposed by effective suppression during seed repair, and the upper limit imposed by bubble generation in the seed-repair solution that can generate voids for the repair layer). The solution generally does not contain any leveler or accelerators. The accelerator is generally avoided as it does not provide adequate seed layer protection against corrosion that can be achieved during wafer immersion in the presence of accelerators. Only strong suppressors or their combination with levelers can provide the needed seed protection before repair.

The repair process begins with the substrate being positioned in the first plating cell and in contact with the plating solution (the seed layer repair solution). A seed layer repair plating or forward bias, generally between about 1 mA/cm2 and about 3 mA/cm2 is applied to the seed layer for a duration of between about 9 seconds and about 55 seconds. Although higher current densities are known to plate faster, higher current densities do not facilitate seed layer repair processes. As such, lower current densities are preferred. The lower current density limit of the seed layer repair plating process is generally imposed by a throughput requirement, i.e., although lower current densities are available, the lower limit is about as low as the process can go while maintaining acceptable commercial throughput. Further, although higher current densities are preferred, the upper limit of the seed layer repair process is generally imposed by the minimization of seed overhang. The duration of the repair process is generally determined by the repair layer thickness and the current density, i.e., the repair layer thickness generally needs to be greater than 200 Å for the subsequent gapfill and it needs to be greater than 100 Å to get continuous smooth repair layer. Further still, the substrate support member and the substrate being plated will generally be rotated during the seed layer repair process at a rate of between about 5 rpm and about 100 rpm. The temperature of the substrate during the plating process is generally between about 10° C. and about 80° C.

Another fundamental step in the seed layer repair process of the invention is the post-seed-repair cleaning to remove the residual additives on wafer surface. Generally, the only additive in the repair solution is the suppressor molecule, so the inventors have demonstrated how the suppressor residual can be removed and how the presence of trace amount of chloride ions prevents the effective cleaning. Because it is almost impossible to fully remove the leveler species from the surface, the inventors have determined that the use of levelers in the repair solution should be avoided, even though the levelers can further enhance the anti-corrosion capability of the repair solution. The only category of organic additives the inventors believe can be effectively added into the repair solutions is the non-ionic surfactant molecules like the suppressors, the wetting agents, and the anti-foaming agents. Wetting agents and anti-foaming agents will also act as secondary suppressors in addition to improving the solution wetting to wafer and reducing the occurrence of gas bubbles during wafer immersion. Generally, wetting agents and anti-foaming agents are based on non-ionic surfactants are legitimate candidates. Due to the weak interaction of the non-ionic surfactants with Cu surface, these additives can be removed from the Cu surface after the repair step is completed with the cleaning method discussed above.

Once the repair and substrate cleaning process has been completed, the substrate may be transferred to a second plating cell where subsequent plating processes may be conducted thereon. More particularly, the second plating cell may be configured with both chemistry and processing parameters to facilitate a gap fill plating process or a bulk fill plating process, for example.

While the foregoing is directed to embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow. 

1. A method for electrolytically repairing a copper seed layer, comprising: positioning the seed layer in fluid communication with a low conductivity seed layer repair solution, the low conductivity seed layer repair solution comprising: a copper concentration of less than about 20 g/l; a pH of less than about 4; a chlorine ion concentration of between about 20 ppm and about 100 ppm; and an additive organic surfactant configured to suppress a copper deposition rate at a concentration of between about 100 ppm and about 2000 ppm; and applying a seed layer repair bias configured to generate a current density of less than about 5 mA/cm² across the seed layer.
 2. The method of claim 1, wherein the pH of the seed layer repair solution is greater than about 1.5.
 3. The method of claim 1, wherein the additive organic surfactant comprises at least one of polyethylene glycol and copolymers of ethylene oxide-propylene oxide.
 4. The method of claim 1, wherein an electrical conductivity of the seed layer repair solution is between about 6 mS/cm and about 20 mS/cm.
 5. The method of claim 1, wherein positioning the seed layer comprises immersing the seed layer into the seed layer repair solution while simultaneously applying a forward immersion bias to the seed layer.
 6. The method of claim 1, wherein the copper concentration is between about 3 g/l and about 10 g/l.
 7. The method of claim 1, wherein the low conductivity seed layer repair solution further comprises between about 0.1 g/l and about 1.0 g/l of acid.
 8. A method for filling a semiconductor feature having a seed layer deposited thereon with a conductive material, comprising: positioning the seed layer in a first plating solution, the first plating solution comprising a pH of between about 1.5 and about 4.0 and a copper concentration of between about 3 g/l and about 10 g/l; applying a first plating bias to the seed layer to plate a metal onto discontinuities in the seed layer, the first plating bias being configured to generate a first current density across the seed layer of less than about 5 mA/cm²; removing the seed layer from the first plating solution; cleaning the seed layer of residual chemical constituents from the first plating with a cleaning solution, wherein the cleaning solution comprises less than about 1 ppm of chlorine ions; positioning the seed layer in a second plating solution, the second plating solution being different from the first plating solution; and applying a second plating bias to the seed layer to deposit a feature fill layer, wherein the second plating bias is configured to generate a second current density across the seed layer that is greater than the first current density.
 9. The method of claim 8, wherein the first plating solution further comprises: a copper concentration of between about 3 g/l and about 20 g/l; a chlorine concentration of between about 20 ppm and about 100 ppm; and an organic surfactant at a concentration of between about 100 ppm and 2000 ppm.
 10. The method of claim 9, wherein the organic surfactant comprises at least one of polyethylene glycol and copolymers of ethylene oxide-propylene oxide.
 11. The method of claim 9, further comprising adding an organic wetting agent based on non-ionic surfactants at a concentration of between about 50 ppm and about 500 ppm.
 12. The method of claim 9, further comprising adding an organic anti-foaming agent based on non ionic surfactant at a concentration of between about 50 ppm and about 500 ppm.
 13. The method of claim 8, wherein cleaning the seed layer further comprises: transferring the substrate to a spin rinse dry cell; rotating the substrate at a rate of between about 400 rpm and about 1000 rpm; and dispensing deionized water onto the seed layer to remove chemical constituents therefrom.
 14. The method of claim 8, wherein positioning the seed layer in the first and second plating solutions further comprises applying a cathodic bias to the seed layer during the immersion process, the cathodic bias being configured to overcome seed layer etching caused by the plating solution.
 15. The method of claim 8, wherein the second plating solution comprises copper ions at a concentration of between about 30 g/l and about 60 g/l, chlorine ions at a concentration of between about 20 ppm and about 100 ppm, an organic plating suppressor additive at a concentration of between about 100 ppm and about 2000 ppm, a leveler additive at a concentration of between about 1 ml/l to about 10 ml/l, and a plating accelerator additive at a concentration of between about 5 ppm and about 60 ppm.
 16. The method of claim 8, wherein the second plating bias is configured to generate a current density of between about 3 mA/cm² and about 10 mA/cm² across a plating surface of the substrate.
 17. The method of claim 8, wherein the first plating solution has a conductivity of between about 5 mS/cm and about 20 mS/cm.
 18. A method for plating a metal onto a discontinuous seed layer, comprising: immersing the seed layer in a low conductivity electrolytic plating solution having a pH of between about 1.5 and about 3.0; applying an electrical bias to the seed layer that is configured to generate a current density of between about 1 mA/cm² and about 5 mA/cm² across the seed layer; removing the seed layer from the low conductivity electrolytic plating solution; rinsing the seed layer of residual chemicals; immersing the seed layer in a conductive gap fill electrolytic solution having a pH of less than about 4; and applying a gap fill bias to the seed layer to electrolytically fill features formed thereon, the gap fill bias being configured to generate a current density of between about 3 mA/cm² and about 10 mA/cm² across the seed layer.
 19. The method of claim 18, wherein immersing the substrate into the low conductivity electrolytic plating solution and the conductive gap fill solution further comprises applying a forward immersion bias to the seed layer during the immersion, the forward immersion bias being configured to overcome etching of the seed layer by the solutions during immersion.
 20. The method of claim 18, wherein the low conductivity electrolytic plating solution further comprises a copper concentration of between about 3 g/l and about 10 g/l and an acid concentration of between about 0.1 g/l and about 2.0 g/l.
 21. The method of claim 20, wherein the low conductivity electrolytic plating solution further comprises an organic suppressor surfactant at a concentration of between about 200 ppm and about 2000 ppm.
 22. A low conductivity electrolytic seed layer repair solution for semiconductor processing, comprising: copper sulfate at a concentration of between about 3 g/l and 20 g/l; acid at a concentration of between about 0.1 g/l and 2 g/l; chlorine ions at a concentration of between about 20 ppm and 70 ppm; and an additive suppressor surfactant at a concentration of between about 200 ppm and 2000 ppm. 